Derivatization of Undecahalogenated -Dodecaborates [BXNH] (X = F-I): Attaching Isocyanate, Amidinium, and Formamide Functionalities.

Halogenated -dodecaborates are very robust and versatile weakly coordinating anions for numerous applications. The introduction of additional substituents, e.g.

Probing fragment ion reactivity towards functional groups on coordination polymer surfaces.

Functionalization of surface-grown coordination polymer layers by ion soft-landing of highly reactive molecular fragment ions is demonstrated. The ions form covalent bonds to terminal functional groups of the polymer at the vacuum interface, opening new perspectives for controlled bond formation using reactive ions.

Spontaneous ligand loss by soft landed [Ni(bpy)] ions on perfluorinated self-assembled monolayer surfaces.

Transition metal (TM) complexes are widely used in catalysis, photochemical energy conversion, and sensing. Understanding factors that affect ligand loss from TM complexes at interfaces is important both for generating catalytically-active undercoordinated TM complexes and for controlling the degradation pathways of photosensitizers and photoredox catalysts. Herein, we demonstrate that well-defined TM complexes prepared on surfaces using ion soft landing undergo substantial structural rearrangements resulting in ligand loss and formation of both stable and reactive undercoordinated species.

Probing the Electronic Structure of [BH] Dianion Encapsulated by an Octamethylcalix[4]pyrrole Molecule.

Despite being an important -borate in condensed phase boron chemistry, isolated [BH] is electronically unstable and has never been detected in the gas phase. Herein, we report a successful capture of this fleeting species through binding with an octamethylcalix[4]pyrrole (omC4P) molecule to form a stable gaseous omC4P·[BH] complex and its characterizations utilizing negative ion photoelectron spectroscopy (NIPES). The recorded NIPE spectrum, contributed by both omC4P and [BH], is deconvoluted by subtracting the omC4P contribution to yield a [BH] spectrum.

Generation and reactivity of the fragment ion [BIS(CN)] in the gas phase and on surfaces.

Gaseous fragment ions generated in mass spectrometers may be employed as "building blocks" for the synthesis of novel molecules on surfaces using ion soft-landing. A fundamental understanding of the reactivity of the fragment ions is required to control bond formation of deposited fragments in surface layers. The fragment ion [BX] (X = halogen) is formed by collision-induced dissociation (CID) from the precursor [BX] dianion.